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Determining the phase-transition temperature is crucial in the design of molten salt reactors, as operational temperatures need to be established considering the safety margins related to the thermodynamic stability of the molten salt system. This study introduces a novel approach to determine the phase-transition temperature based on rapid electrical conductivity measurements using a microsecond-scale staircase voltammetry technique. The phase-transition temperature is determined near distinct points where the electrical conductivity abruptly changes, indicating phase transitions. The phase-transition temperatures of three LiCl–KCl molten salt systems, determined using the proposed approach based on electrical conductivity measurements, are with relative errors less than 3% compared with reported phase transition data based on conventional thermal analysis techniques.